Homonuclear amino-alphylamion-anthraquinone sulphonic acids and process of making the same



Patented Nov. 12, 1929 UNITED STATES PATENT OFFICE KLAUS WEINAND, OF FLITTARD, NEAR GOLOGNE-ON-THE-RHINE, GERMANY, ASSIGNOR TO GENERAL ANILINE WORKS, INC., 015 NEW YORK, N. Y., A CORPORATION OF DELAWARE HOIMIONUOLEAR AMINO-ALPHYLAMINO-ANTHRAQUINONE SULPHONIC ACIDS AND PROCESS OF MAKING THE SAME No Drawing. Application filed August 18, 1926, Serial No. 130,112, andin Germany August 21, 1925.

My invention consists in novel dyestulfs which are homonuclear l-amino--alkylamino-anthraquinone sulphonic acids and in processes of making the same.

It is well known that by acting with aromatic amines in presence of catalysts, such as Homonuclear amino arylamino substituted anthraquinone sulphonic acids are described for instance in U. S. Letters Patent 1,131,516, dated March 9, 1915.

I have now found that by acting with aliphatic, open carbon chain amines, or alkyl amines upon homonuclear et-halogeno, particularly chloro and bromo, 1-amino-anthraquinone sul honic acids new products are obtained whic are homonuclear l-alkylaminol-amino-anthraquinone sulphonic acids.

The term homonuclear is used herein in its usual significance; that is to say, meaning all substituents located in the same benzene nucleus of the anthraquinone molecule, and the term alkyl designates a radicle in which the carbon atom attached to the amino nitrogen is a link in an open chain of carbon atoms, the methyl and methylene radicles being considered the lowest members in the series of open carbon chains. This type of alkyl radicles can be exemplified by methyl, ethyl, propyl, butyl, benzyl, etc. It is thusevident that the term alkyl is used in its generic sense to include those alkyl radicles having an arcmatic substituting group.

This reaction proceeds easily in aqueous solution or suspension even at atmospheric pressure in presence of a copper catalyst, which may be metallic copper itself, mineral acid copper salts or other copper compounds.

The alkyl amines, used in my novel process are much stronger bases than the aromatic bases used heretofore for substitutions in the anthraquinone nucleus, it was therefore quite unexpected that they would react predominently and selectively with the halogen atoms whereas the quite labile sulfo group in the molecule is substantially not attacked.

Amongst the products particularly suited to be used in my novel reaction I might mention the l-aminol-bromo-Q-anthraquinone sulphonic acid and as very valuable products t h e 1-amino-l-alkylamino-2-anthraquinone sulphonic acids.

My novel compounds are blue colored, crystalline substances, soluble in water with the blue colors. The dye animal fibres blue, fast shades. They are distinguished from similar amino arylamino anthraquinone sulphonic acid by the much clearer and brighter shades they produce in the dyeing of wool.

The following examples will further illus trate my invention, the parts being by weight.

EwampZe 1.20 parts l-amino-l-bromo-Q- anthraquinone sulphonic acid, 12 parts sodaash and 1 part copper sulphate are dissolved at 7080 C. in 1000 parts water and 60 parts n-butylamine is added. The solution is heated in an apparatus equipped with a reflux condenser to 8090 C. The solution turns quickly an intense blue and the condensation is finished after about an hours heating. The reaction mass is then acidified and the l-amino- 4-11-butylamino-2-anthraquinone sulphonic acid separates as blue, crystalline needles. It is isolated in the usual manner. It dyes wool particularly clear, greenish-blue shades and has most probably the formula NH: Q00 SOaH O0 Emample Q.-20 parts 1-aminol-bromo-2- anthraqinone sulphonic acid, 12 parts soda ash, 1 part copper sulfate and 60 parts benzylamine are dissolved in a solution of 100 parts pyridine and 900 parts water, and heated for about one hour at 80-90 C. The reaction mass quickly turns blue, it is then acidified and the 1-amino-4-benzylamino-2- anthraquinone sulphonic acid separates. Instead of acidifying one can also steam oflr the pyridine and excess benzylamine and salt out the l-amino-t-benzylamino 2 anthraquinone sulphonic acid. It crystallizes in blue needles and dyes Wool particularly clear reddishblue shades; It has most probably the formula:

5 oo ,som

Y Nn-cm-O I claim:

l. The process of reacting with alkylamines in presence of a copper catalyst upon homonuclear l-aminol-halogeno-anthraquinone 3 sulphonic acids. I

2. The process of reacting with alkylamines in presence of a copper catalyst upon l-aminol-ha-logeno-2-anthraquinone sulphonic. acid.

3. The process of reacting with alkylainines o inpresence of a copper catalyst upon l-amino- -halogeno-Q-anthraquinone sulphonic acid in which the halogen is one of the group com- 7 prising chlorine and bromine.

4. The process of heating an aqueous solu- 25 tion of 1-amino--bromo-2-anthraquinone sulphonic acid with an alkylamine in presence of a copper catalyst.

5. The process of heating an aqueous solution of l-amino--bromo-EZ-anthraquinone a0 sulphonic acid with n-butylamine in presence of copper sulfate. 1

6. As new products homonuclear l-amino- -alkylamino-anthraquinone sulphonic acids, the alkyl-groups of which contain more than 35 onecarbon-atom, which are blue crystalline substances, dyeing wool particularly clear, blue shades.

7. As new products 1-amino-4-alkylamino- 2-anthraquinone sulphonic acids, the alkyl- 40 groups of which contain more than one carhon-atom, which are blue crystalline substances, dyeing Wool particularly clear, blue shaldes and having most probably the formu a:

NHz

\ I oo 5B NH-ALKYL 8. As anew product the l-amino-l-n-butyli mino-Q-anthraquinone sulphonic acid, which crystallizes in blue needles, is soluble in water with a blue color, dyes wool particularly clear, greenish-blue shades and has most probably the formula NE-OHs-flEa-CHa-Oli'n In testimony whereof, I afix my signature. c5 KLAUS WEINAJN D, 

